COMPOUND-I AND COMPOUND-II ANALOGS FROM PORPHOLACTONES

The tetraaza macrocycles 2-oxa-3-oxotetramesitylporphine (\H-2 1\) and 2-oxa-3-oxotetrakis (2,6-dichlorophenyl)-porphine (\H-2 2\) and the c orresponding iron complexes (\Fe-III(X) 1\ and \Fe-III(X) 2\; X= Cl-, OH-, or SO3CF3-) have been synthesized. These macrocycles are derived from porphyrins by transformation of one pyrrole ring to an oxazolone ring. The resulting lactone functionality serves to restrict but not c ompletely block pi-conjugation around the periphery. These complexes t hus share properties with both porphyrins and chlorins. The ferric and high-valent iron complexes have been characterized by a variety of sp ectroscopic techniques. The molecular structure of Fe-III(Cl) 2\ has b een obtained by X-ray crystallography and shows that the structural ch anges at the macrocycle periphery do not perturb the coordination sphe re of iron relative to the corresponding porphyrin complexes. This is illustrated by the observation that Fe-O frequencies in the resonance Raman spectra of the porpholactone analogues of compounds I and II are not substantially different from those of porphyrins and by the axial appearance of the EPR signals of the high-spin ferric complexes. This is consistent with reports that the Fe=O unit of oxidized porphyrins and chlorins is relatively insensitive to alteration of macrocycle sym metry. Nevertheless, probes of properties of the porpholactone macrocy cle (H-1 NMR, resonance Raman skeletal modes) show effects of the asym metry induced by the oxazolone ring. On the basis of H-1 NMR, EPR, Mos sbauer, and resonance Raman data, the singly occupied molecular orbita l of oxoferryl porpholactone pi-cation radicals correlates with the a( 1u) molecular orbital of porphyrins under D-4h symmetry. Moreover, the paramagnetic properties and the intramolecular exchange interaction o f ferryl iron and the porpholactone pi-radical have been characterized by EPR and magnetic Mossbauer measurements and spin-Hamiltonian analy ses. The values J(0) = 17 cm(-1) and J(0) = 11 cm(-1) obtained for the exchange coupling constants of the oxoferryl porpholactone pi-cation radical complexes \Fe-IV=O 1\(+) and \Fe-IV=O 2\(+), respectively, are among the lowest found for synthetic compound I analogues.